CN102650824A - Forming method of pixel pattern, color filter, display element and coloring radioactive ray sensitive composite - Google Patents

Abstract

The invention relates to a forming method of pixel patterns, a color filter, a display element and a coloring radioactive ray sensitive composite. Dyes and mordant pigments are used as colorant in the forming method of pixel patterns whose good chroma feature of dyes is fully shown. The forming method of pixel patterns comprises the steps of forming a coating of coloring radioactive ray sensitive composites which have at least one of dyes and mordant pigments on a substrate; exposing at least a part of the coating by means of ultraviolet LEDs.

Description

Formation method, color filter, display element and the colored radiation-sensitive composition of pattern of pixels

Technical field

The present invention relates to pattern of pixels the formation method, possess the color filter, the display element that possesses this color filter and the colored radiation-sensitive composition that adopt the pattern of pixels that this method forms.

Background technology

Color filter produces painted transmitted light through the transmittance that makes the particular wavelength region in the visible light.Though use the liquid crystal display cells of liquid crystal himself can not develop the color, can bring into play function as color liquid crystal display device through using color filter.And color filter also is used to have used colored demonstrations such as organic EL (electroluminescence, Electro Luminescence) element, Electronic Paper of white luminous layer.And then, if utilize color filter, just can realize the colour phhotograpy of solid-state imagers such as ccd image sensor, cmos image sensor.

As manufacturing method of color filter, known following method.For example, on the transparency carrier or formed coating colored radiation-sensitive composition conduct on the transparency carrier of light shield layer that institute hopes pattern plays induction to suitable radioactive ray coloured composition.Then, will film and carry out after the drying, and be situated between and by mask dry coating to be shone radioactive ray (below, be called " exposure ") and to implement development treatment, the method that obtains each color pixel thus is (for example, with reference to patent documentation 1 and 2.)。And also known use colored curable resin composition and the method etc. that obtains each color pixel through ink-jetting style are (for example, with reference to patent documentation 3.)。

But, the high-definition of the known high brightnessization that will realize display element and high color purityization or solid-state imager, using dyestuff or mordant pigment is effectively (for example, with reference to patent documentation 4 and 5) as colorant.

[prior art document]

[patent documentation]

[patent documentation 1] japanese kokai publication hei 2-144502 communique

[patent documentation 2] japanese kokai publication hei 3-53201 communique

[patent documentation 3] TOHKEMY 2000-310706 communique

[patent documentation 4] TOHKEMY 2008-304766 communique

[patent documentation 5] TOHKEMY 2001-081348 communique

Summary of the invention

But, contain the colored radiation-sensitive composition of dyestuff, mordant pigment and compare, the remarkable deterioration of the technology stability of colorimetric properties with the colored radiation-sensitive composition that only contains pigment.Therefore, even adopt dyestuff, mordant pigment as colorant, the result also can exist and be difficult to obtain to the problem of pigment at the color filter that has superiority aspect the colorimetric properties.

The present invention accomplishes in view of above such problem.That is, the objective of the invention is to, be provided at the formation method and the excellent display element of colorimetric properties that are used to make the pattern of pixels that the excellent colorimetric properties of dyestuff appear fully when using dyestuff, mordant pigment as colorant.

The inventor is through concentrating on studies, and the result finds: when forming pattern of pixels, through utilizing ultraviolet LED as exposure light source, can solve above-mentioned problem.

That is, the present invention provides a kind of formation method of pattern of pixels, and it comprises: (1) forms the operation of filming of colored radiation-sensitive composition on substrate, said colored radiation-sensitive composition contains at least a kind that is selected from dyestuff and the mordant pigment; And (2) operation of adopting ultraviolet LED that above-mentioned at least a portion of filming is made public.

And; The present invention provides: the color filter with the pattern of pixels that adopts said method formation; Possess the display element of this color filter, and contain (A) and contain at least a kind colorant being selected from dyestuff and the mordant pigment, (B) resin glue, (C) crosslinking chemical, colored radiation-sensitive composition (D) Photoepolymerizationinitiater initiater, that be used for forming pattern of pixels through ultraviolet LED exposure.

According to the present invention, can be manufactured on the color filter of the colorimetric properties of bringing into play dyestuff, mordant pigment excellence when using dyestuff, mordant pigment fully as colorant.

Embodiment

Below, this embodiment is at length explained.

< the formation method and the color filter of pattern of pixels >

The formation method of pattern of pixels of the present invention is a characteristic with the operation that comprises following (1) and (2) at least.

(1) the operation of filming that forms the colored radiation-sensitive composition contain dyestuff on the substrate (below be also referred to as " film and form operation ")

(2) adopt the operation that ultraviolet LED makes public to above-mentioned at least a portion of filming (below be also referred to as " exposure process ")

Below, for each operation of (1) and (2), enumerate object lesson and be elaborated.

(1) the formation operation of filming

At first, prepared substrate.As substrate, can use transparent glass substrates such as pyrex, alumina borosilicate glass, alkali-free glass, quartz glass, synthetic quartz glass, soda-lime glass, corundum.In addition, can also use acrylic compounds, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, PEN, triacetyl cellulose, syndiotactic polytyrene, polyphenylene sulfide, polyetherketone, polyetheretherketone, fluororesin, polyethers nitrile, polycarbonate, Noryls such as polymethylmethacrylate, gather cyclohexene, polynorbornene is transparent resin films such as resin, polysulfones, polyethersulfone, polyarylate, polyamidoimide, polyetherimide or TPI.Alkali-free glass particularly, it is the coefficient of thermal expansion materials with smaller, considers and preferred use from dimensional stability and the excellent aspect in the high-temperature heating treatment.

In addition; Also can be as required these substrates be implemented to adopt agent treated, the plasma treatment of silane coupling agents etc., in addition can also implement to adopt the suitable pre-treatments such as film forming of the silicon dioxide film of ion plating method, sputtering method, gas-phase reaction method or vacuum vapour deposition etc. in advance.

Then, on substrate, form light shield layer (black matrix) with the mode that marks off the part that forms pixel.For example, utilize the photoetching process will be through sputter, vapor deposition and the metallic films such as chromium of film forming are processed into desirable pattern.Perhaps, can the radiation-ray sensitive composition that contain black colorant be coated on the substrate, adopt photoetching process to form desirable pattern.Thickness by the film formed light shield layer of metal foil is preferably 0.1 μ m～0.2 μ m usually.On the other hand, use the radiation-ray sensitive composition of black and the thickness of the photomask that forms is preferably about 1 μ m.

In addition, the situation that does not need light shield layer is arranged also, the operation that forms light shield layer in this case can be omitted.

Then, coating for example contains blue radiation-ray sensitive composition blue dyes, minus on aforesaid substrate.Then, thus carrying out prebake forms solvent evaporation to film.

When colored radiation-sensitive composition is coated substrate, can suitably select spray-on process, rolling method, method of spin coating (spin-coating method), slot die rubbing method or excellent Tu Fa etc.Consider from this point of filming that obtains homogeneous film thickness, preferably adopt spin-coating method or slot die rubbing method.

Prebake makes up drying under reduced pressure usually and heat drying carries out.Drying under reduced pressure proceeds to usually and reaches 50Pa～200Pa.In addition, the condition of heat drying normally adopts heating plate, is carrying out about 1 minute～10 minutes under 70 ℃～110 ℃ the temperature.In addition, the thickness of filming that is coated with is generally 0.6 μ m～8.0 μ m with dried film thickness gauge, preferred 1.2 μ m～5.0 μ m.

In addition, as other example of filming that on substrate, forms colored radiation-sensitive composition, can also enumerate the method that japanese kokai publication hei 7-318723 communique, TOHKEMY 2000-310706 communique etc. are disclosed, adopt ink-jetting style.In the method, at first, on the surface of substrate, form the next door that also has shade function concurrently.The colored radiation-sensitive composition that then, will for example contain blue dyes through ink discharge device is ejected in this next door.Afterwards, carry out prebake and make solvent evaporation.The method of prebake is identical with the first above-mentioned example with condition.

Should explain that shade function is not only brought into play in above-mentioned next door, also performance is used to make the colored radiation-sensitive composition of all kinds that is ejected in the dividing regions that the function of colour mixture does not take place.Therefore, compare with the light shield layer that uses in above-mentioned first example (black matrix), thickness is thicker.The next door uses the radiation-ray sensitive composition of black to form usually.

In addition, as the further example of filming that on substrate, forms colored radiation-sensitive composition, can also enumerate disclosed dry film methods such as japanese kokai publication hei 9-5991 communique.In the method, coating for example contains the colored radiation-sensitive composition of blue dyes on membranaceous supporter, makes organic solvent evaporation through carrying out prebake, thereby is manufactured on the dry film that is formed with colored radiation-sensitive composition on the supporter.Then, utilizing laminator that this support body layer that is formed with the colored radiation-sensitive composition layer is closed in color filter forms on the substrate of usefulness.Afterwards, the colored radiation-sensitive composition layer is peeled off from supporter, thereby the colored radiation-sensitive composition layer is transferred on the substrate.The method of the method for coating colored radiation-sensitive composition, prebake and condition are identical with the first above-mentioned example on supporter.

(2) exposure process

After the formation operation of filming, be situated between usually and formed at least a portion of filming made public by photomask with predetermined pattern.The exposure light source that the present invention utilized with this moment is that ultraviolet LED is as characteristic.Ultraviolet ray LED is meant the light emitting diode that sends ultraviolet light.As available ultraviolet LED; As long as state the just special restriction of nothing of ultraviolet light that Photoepolymerizationinitiater initiater carries out sensitization after sending; But obtain the extremely excellent color filter of colorimetric properties, just preferably send peak wavelength more than 300nm, especially at the ultraviolet LED of the ultraviolet light of 350nm～400nm scope.In the present invention, supposition can suppress the dyestuff degraded in the exposure process through making the ultraviolet LED with said characteristics of luminescence become exposure light source.At this, " peak wavelength " is meant the maximum wavelength of luminous intensity in luminescent spectrum, can adopt commercially available spectrophotometer to measure.

Exposure in the formation method of pattern of pixels of the present invention is generally 10～10,000J/m ²In addition, as its illumination, use 10mW/cm usually ²Above illumination.As ultraviolet LED irradiation unit, commercially available by for example Matsushita Electric Industrial Co., Ltd.

After the above-mentioned exposure process, carry out the operation that will film and cure after carrying out in the operation that (3) filming after will making public develop (below be also referred to as " developing procedure ") and/or (4) as required.

(3) developing procedure

After the exposure process, adopt developer solution to develop, the unexposed portion of filming is removed in dissolving thus.As developer solution; Preferred alkaline-based developer for example, uses sodium carbonate, NaOH, potassium hydroxide, TMAH, choline, 1; 8-diazabicyclo-[5.4.0]-7-undecylene, 1, the WS of 5-diazabicyclo-[4.3.0]-5-nonene etc.Also can add for example water-miscible organic solvent such as methyl alcohol, ethanol, surfactant etc. in right amount by the alkalitropism developer.In addition, alkaline development is washed after handling usually.

As the development treatment method, can use spray development method, spray development method, dipping (dip) development method or soak and put (liquid pool) development method etc.Development conditions for example can be to carry out for 5 second～300 seconds at normal temperatures.

In addition, when adopting above-mentioned ink-jetting style to form filming of colored radiation-sensitive composition, owing to not needing developing procedure and with its omission.

(4) operation that will film and cure after carrying out

After the developing procedure, perhaps adopt above-mentioned ink-jetting style to form to film and, consider, preferably will form and cure after filming of pattern carried out from improving this point of curable through after the exposure process.When adopting hot-blast heater, after the condition of curing for example can be to carry out about 20 minutes～40 minutes under 150 ℃～250 ℃.

So, can form and contain pel array blue dyes, that the blue pixel pattern is arranged with the regulation alignment arrangements.Then; Use the green radiation-ray sensitive composition of minus, repeat above-mentioned operation, on same substrate, form green pattern of pixels thus; Further use the red radiation-ray sensitive composition of minus; Repeat above-mentioned operation, on same substrate, form red pattern of pixels thus, can make the color filter that redness, green and blue trichromatic pattern of pixels are arranged with the regulation alignment arrangements thus.But in this embodiment, the order that on substrate, forms pattern of pixels of all kinds is not limited to above-mentioned example.Formation order of all kinds can suitably change.

The thickness of the pattern of pixels that as above forms is generally 0.5 μ m～5.0 μ m, is preferably 1.0 μ m～3.0 μ m.

In addition, in the present invention, the pattern of pixels that constitutes color filter is not limited to redness, green and blue, also can be to be trichromatic pattern of pixels with yellow, carmetta and cyan.In addition, except with the corresponding colored pattern of trichromatic pixel, can also form the 4th, the 5th colored pattern.For example; Disclosed like Japan special table 2005-523465 communique etc.; Except with red, green and the blue corresponding colored pattern of trichromatic pixel, can also dispose the 4th pixel (yellow pixel), the 5th pixel (cyan pixel) that are used to enlarge chromaticity range.

Can be through further on the pattern of pixels that forms like this, the display characteristic that diaphragm improves display element being set.As diaphragm, can enumerate the organic membrane or organic-inorganic hybrid films or the inoranic membranes such as SiNx film and SiOx film that form by solidification compound.In this embodiment, preferably form diaphragm with solidification compound.

As the method that forms diaphragm with hardening resin composition, for example can adopt disclosed methods such as japanese kokai publication hei 4-53879 communique or japanese kokai publication hei 6-192389 communique.

As the hardening resin composition that is used to form diaphragm, for example can enumerate disclosed hot curing resin compositions such as japanese kokai publication hei 3-188153 communique or japanese kokai publication hei 4-53879 communique; Disclosed radiation sensitive resin compositions such as japanese kokai publication hei 6-192389 communique or japanese kokai publication hei 8-183819 communique; The disclosed solidification compounds that contain polysiloxane such as TOHKEMY 2006-195420 communique or TOHKEMY 2008-208342 communique etc.

According to the formation method of pattern of pixels of the present invention, can obtain harmless lost territory performance dyestuff, the excellent higher color filter of values (Y) colorimetric properties, that be brightness in excitation and the cie color system of mordant pigment.Therefore, can obtain the excellent color filter of colorimetric properties through the formation method that adopts pattern of pixels of the present invention.The formation method of pattern of pixels of the present invention for example is suitable for making with color liquid crystal display device with the color separation of color filter, solid-state imager with color filter, organic EL display element with color filter, Electronic Paper with the various color filters headed by the color filter, is particularly suited for making and uses the color liquid crystal display device of large substrate to use color filter.

< colored radiation-sensitive composition >

In the formation method of pattern of pixels of the present invention, use and contain at least a kind the colored radiation-sensitive composition that is selected from dyestuff and the mordant pigment.This colored radiation-sensitive composition contains at least: (A) contain at least a kind colorant being selected from dyestuff and the mordant pigment, (B) resin glue, (C) crosslinking chemical and (D) Photoepolymerizationinitiater initiater.Below, each composition is described.

-(A) colorant-

Employed colored radiation-sensitive composition contains at least a kind of conduct (A) colorant that is selected from dyestuff, the mordant pigment in the formation method of pattern of pixels of the present invention.As dyestuff, there is not restriction especially, for example can enumerate azo based dye, anthraquinone based dye, xanthene based dye, triarylmethane based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, methine based dye etc.Can enumerate dyestuff particularly with color index (C.I.) name that is described below.

C.I. acid yellow 11; C.I. acid orange 7; C.I. acid red 37; C.I. acid red 18 0; C.I. acid blue 29; C.I. solvent blue 89; C.I. directly red 28; C.I. directly red 83; C.I. direct yellow 12; C.I. direct orange 26; C.I. direct green 28; C.I. direct green 59; C.I. reactive yellow 2; C.I. reactive red 17; C.I. reactive red 120; C.I. disperse orange 5; C.I. disperse red 58; C.I. disperse blue 165; C.I. alkali blue 41; C.I. Basic Red 18; C.I. mordant rouge 7; C.I. mordant yellow 5 based dyes such as azo such as grade;

C.I. anthraquinone based dyes such as vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60;

C.I. alkaline red, C.I. alkali red 1:1: 1, xanthene based dye such as C.I. alkaline purple 10, C.I. solvent red 49;

C.I. triarylmethane based dye such as Blue 7, C.I. alkali blue 11;

C.I. vat blue 5 based dyes such as phthalocyanine such as grade;

C.I. quinone imines based dye such as alkali blue 3, C.I. alkali blue 9;

C.I. quinoline based dyes such as solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64;

C.I. nitro based dyes such as Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42;

C.I. solvent yellow 179 based dyes such as methine such as grade.

In addition, can also enumerate the azo based dye of the records such as claim 3 or claim 4, TOHKEMY 2010-170073 communique, TOHKEMY 2010-170074 communique, TOHKEMY 2010-275531 communique, TOHKEMY 2010-275533 communique of TOHKEMY 2010-168531 communique; The triarylmethane based dye of records such as the claim 14 of Japan special table 2007-503477 communique, No. 10/123071 communique of International Publication; The xanthene based dye of record such as TOHKEMY 2010-244027 communique, TOHKEMY 2010-254964 communique etc.

Among these dyestuffs, consider preferred azo based dye, triarylmethane based dye, xanthene based dye, methine based dye from manufacturing method of color filter of the present invention, obtaining this point of excellent especially effect.

In the present invention, dyestuff can use separately, perhaps mixes more than 2 kinds and uses.

In addition, mordant pigment is meant through precipitation agent and makes the dyestuff of solubility become the material that insoluble pigment gets.As precipitation agent, for example can enumerate barium chloride, lime chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, synthetic mordant Catanol, synthetic mordant Tamol, isopolyacid, heteropoly acid (for example phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, silicon tungsten molybdic acid, silico-tungstic acid, silicomolybdic acid) etc.Among these, as precipitation agent, preferred isopolyacid, heteropoly acid.

As such mordant pigment, can enumerate pigment with color index (C.I.) name that is described below.

C.I. pigment blue 1, C.I. alizarol saphirol 2, C.I. alizarol saphirol 3, C.I. alizarol saphirol 9, C.I. pigment blue 10, C.I. pigment blue 14, C.I. pigment blue 1 7:1, C.I. alizarol saphirol 24, C.I. alizarol saphirol 24:1, C.I. alizarol saphirol 56, C.I. pigment Blue-61, C.I. alizarol saphirol 62;

C.I. pigment violet 1, C.I. pigment violet 2, C.I. pigment violet 3, C.I. pigment violet 3: 1, C.I. pigment violet 3: 3, C.I. pigment violet 27, C.I. pigment violet 39;

C.I. naphthol green 1, C.I. naphthol green 4;

C.I. pigment red 4 8:1; C.I. pigment red 4 8:2; C.I. pigment red 4 8:3; C.I. pigment red 4 8:4; C.I. pigment red 4 8:5; C.I. pigment red 49; C.I. pigment red 4 9:1; C.I. pigment red 4 9:2; C.I. pigment red 4 9:3; C.I. paratonere 52:1; C.I. paratonere 52:2; C.I. paratonere 53:1; C.I. paratonere 54; C.I. paratonere 57:1; C.I. paratonere 58; C.I. paratonere 58:1; C.I. paratonere 58:2; C.I. paratonere 58:3; C.I. paratonere 58:4; C.I. paratonere 60:1; C.I. paratonere 63; C.I. paratonere 63:1; C.I. paratonere 63:2; C.I. paratonere 63:3; C.I. paratonere 64:1; C.I. paratonere 68; C.I. pigment red 81; C.I. pigment red 81: 1; C.I. paratonere 200; C.I. paratonere 237; C.I. paratonere 239; C.I. paratonere 247;

C.I. pigment yellow 61, C.I. pigment yellow 61:1, C.I. pigment yellow 62, C.I. pigment yellow 100, C.I. pigment yellow 104, C.I. pigment yellow 13 3, C.I. pigment yellow 168, C.I. pigment yellow 169, C.I. pigment yellow 183, C.I. pigment yellow 191, C.I. pigment yellow 191:1, C.I. pigment yellow 206, C.I. pigment yellow 209, C.I. pigment yellow 209:1, and C.I. pigment yellow 212.

Among these mordant pigments; Consider that from the formation method of pattern of pixels of the present invention, obtaining this point of excellent especially effect triarylmethanes such as preferred C.I. pigment blue 1, C.I. alizarol saphirol 2, C.I. alizarol saphirol 3, C.I. alizarol saphirol 9, C.I. pigment blue 10, C.I. pigment blue 14, C.I. alizarol saphirol 62, C.I. pigment violet 1, C.I. pigment violet 2, C.I. pigment violet 3, C.I. pigment violet 27, C.I. pigment violet 39 are mordant pigment.Is that mordant pigment is also open by for example TOHKEMY 2011-150195 communique, TOHKEMY 2011-186043 communique etc. with isopolyacid or heteropoly acid as the triarylmethane of precipitation agent.

In the present invention, mordant pigment can use separately, perhaps mixes more than 2 kinds and uses.

In the present invention, as colorant, can also use other colorant with above-mentioned dyestuff and mordant pigment.As other colorant, there is not restriction especially, can come suitably to select color, material according to the purposes of color filter.Particularly, also can use in organic pigment, inorganic pigment and the natural colouring matter any as colorant.Consider from the high excitation of needs, brightness and contrast, preferably use organic pigment.

As the preferred object lesson of organic pigment; With the expression of color index (C.I.) name, can enumerate C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 1, C.I. pigment blue 15: 6, C.I. alizarol saphirol 80, C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. pigment yellow 211, C.I. pigment orange 38, C.I. pigment orange 23 etc.

Consider from forming this point of the excellent pixel of brightness height and excitation, usually in the solid state component of colored radiation-sensitive composition (A) colorant contain proportional to be 5～70 quality %, to be preferably 5～60 quality %.Said here solid state component be meant except that after composition the solvent stated.

In addition, being selected from least a in dyestuff and the mordant pigment, to contain proportional preferably be more than the 5 quality %, more than 10 quality % in all coloring agent.

-(B) resin glue-

As (B) resin glue among the present invention, do not have restriction especially, but preferably have the resin of acidic functionalities such as carboxyl, phenol property hydroxyl, sulfo group.In order to improve the desirable effect of the present invention, preferably all containing more than the 10 quality % in the resin glues, further preferably containing the polymkeric substance more than the 30 quality % with acidic functionality and polymerism unsaturated group.Consider that from the viewpoint of colored radiation-sensitive composition storage stability the upper limit of said polymer content is 90 quality % preferably, is preferably 80 quality % especially in whole resin glues.

As above-mentioned acidic functionality, can enumerate carboxyl, phenol property hydroxyl, sulfo group etc., consider preferred carboxyl from the storage stability aspect of the colored radiation-sensitive composition of alkali-soluble and gained.

In addition,, can enumerate ethenyl aromatic yl, (methyl) acryloyl group, allyl etc., consider preferred (methyl) acryloyl group from improving this point of desirable effect as above-mentioned polymerism unsaturated group.In addition, the polymkeric substance that has acidic functionality and a polymerism unsaturated group preferably has the polymerism unsaturated group at its side chain.

Satisfy above-mentioned necessary condition and just do not have special restriction as long as have the polymkeric substance of acidic functionality and polymerism unsaturated group, for example can enumerate (b-1) make have Oxyranyle polymerizable unsaturated compound with the carboxyl reaction of the polymkeric substance of polymerizable unsaturated compound with carboxyl polymkeric substance (below be also referred to as " resin glue (b-1) "); (b-2) make polymerizable unsaturated compound with NCO with the hydroxyl reaction of the polymerizable unsaturated compound with hydroxyl and the multipolymer of polymerizable unsaturated compound with acidic functionality polymkeric substance (below be also referred to as " resin glue (b-2) "); (b-3) make polymerizable unsaturated compound with the also oxirane group reaction of the polymkeric substance of polymerizable unsaturated compound, further make the polymkeric substance that acid anhydrides obtains with the hydroxyl reaction that is generated by this reaction (below be also referred to as " resin glue (b-3) ") with Oxyranyle with carboxyl; (b-4) make the epoxy reaction of polymerizable unsaturated compound with carboxyl and epoxy resin, further make the polymkeric substance that acid anhydrides obtains with the hydroxyl reaction that is generated by this reaction (below be also referred to as " resin glue (b-4) "); (b-5) make the copolymer reaction of polymerizable unsaturated compound with hydroxyl and styrene or derivatives thereof and maleic acid or its ester and polymkeric substance of obtaining (below be also referred to as " resin glue (b-5) ") etc.

Be used to make resin glue (b-1) if, the polymkeric substance of polymerizable unsaturated compound with carboxyl has carboxyl does not just have special restriction, be the polymerizable unsaturated compound with carboxyl is carried out polymerization and obtains.

As polymerizable unsaturated compound with carboxyl, for example except that (methyl) acrylic acid, the maleic acid, can also enumerate make lactone and (methyl) acrylic acid carry out addition and unsaturated compound; The unsaturated compound that makes succinic acid, maleic acid, phthalic acid or their dibasic acid such as acid anhydrides or its acid anhydrides and hydroxyalkyl (methyl) acrylic ester carry out addition and get etc.They can use multiple.

Wherein, preferred (methyl) acrylic acid, mono succinate [2-(methyl) acryloxy ethyl] ester (2-(meth) acryloyloxy ethyl succinic acid), ω-carboxyl polycaprolactone list (methyl) acrylic ester, further preferred (methyl) acrylic acid.

As being used to make polymerizable unsaturated compound resin glue (b-1), that have Oxyranyle; For example can enumerate (methyl) glycidyl acrylate, allyl glycidyl ether, α-Yi Jibingxisuan ethylene oxidic ester, crotonyl glycidol ether, (different) crotonic acid glycidol ether, N-(3,5-dimethyl-4-glycidyl) benzyl acrylic amide, (methyl) acrylic acid 4-hydroxyl butyl ester glycidol ether, vinyl benzyl glycidol ether etc. had the unsaturated compound of glycidyl; Have 2,3-epoxide ring amyl group, 3,4-epoxycyclohexyl, 7, the unsaturated compound of polymerism unsaturated groups such as 8-epoxy (three rings [5.2.1.0] last of the ten Heavenly stems-2-yl) ester ring type epoxy radicals such as group and (methyl) acryloyl group.They can use multiple.

As being used to make polymerizable unsaturated compound resin glue (b-2), that have hydroxyl; Except that (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid hydroxy propyl ester, glycerine list (methyl) acrylic ester etc. (methyl) acrylic acid hydroxyalkyl acrylate, can also enumerate N hydroxymethyl acrylamide, allyl alcohol etc.In addition, make polymerizable unsaturated compound resin glue (b-2), that have acidic functionality, can enumerate polymerizable unsaturated compound that enumerated, that have carboxyl etc. in above-mentioned resin glue (b-1) as being used to.They can use multiple.

As being used to make polymerizable unsaturated compound resin glue (b-2), that have NCO; For example can enumerate 2-(methyl) acrylyl oxy-ethyl isocyanates, (methyl) acrylic acid 2-(2-isocyanates base oxethyl) ethyl ester, 1,1-(two acryloyl-oxy methyl) ethyl isocyanate etc.They can use multiple.

Be used to make polymerizable unsaturated compound resin glue (b-3), that have Oxyranyle so long as have the polymkeric substance of Oxyranyle and get final product, can enumerate and have gathering (methyl) acrylic ester based copolymer, having the polystyrenic copolymer of Oxyranyle etc. of Oxyranyle.(methyl) acrylic ester based copolymer that gathers with Oxyranyle is to have (methyl) acrylic acid of Oxyranyle and the multipolymer of other polymerizable unsaturated compound.As (methyl) acrylic ester with Oxyranyle; Can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid 3; 4-epoxy butyl ester, (3, the 4-epoxycyclohexyl) methyl (methyl) acrylic ester, (methyl) acrylic acid 4-hydroxyl butyl ester glycidol ether etc.They can use multiple.

In addition; Phenylethylene styrene based copolymer, that have Oxyranyle that has Oxyranyle as formation; Can enumerate adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, 2; 4-2-glycidyl oxygen ylmethyl styrene, 3,4,5-triglycidyl group methyl styrene etc. has the phenylethylene of 1～3 glycidyl.They can use multiple.

Make polymerizable unsaturated compound resin glue (b-3), that have carboxyl as being used to, for example can enumerate (methyl) acrylic acid, ω-carboxyl-polycaprolactone list (methyl) acrylic ester, mono succinate (2-(methyl) acryloxy ethyl) ester etc.They can use multiple.

As the acid anhydrides that is used to make resin glue (b-3); For example can enumerate malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, anhydride diethylene glycol, phthalic anhydride, cyclohexane-1; 2-dicarboxylic anhydride, 4-cyclohexene-1, the acid anhydrides of polyprotonic acids such as 2-dicarboxylic anhydride, biphenyl acid anhydrides.They can use multiple.

In addition; Making the employed polymkeric substance with polymerizable unsaturated compound of carboxyl of resin glue (b-1), making that resin glue (b-2) is employed to have the multipolymer of the polymerizable unsaturated compound of hydroxyl and the polymerizable unsaturated compound with acidic functionality and make in the polymkeric substance of the employed polymerizable unsaturated compound with Oxyranyle of resin glue (b-3), can make and to carry out copolymerization with other polymerizable unsaturated compound of each polymerizable unsaturated compound copolymerization.

As described other polymerizable unsaturated compound, for example can enumerate N-position substituted maleimide amine such as N-phenylmaleimide, N-cyclohexyl maleimide; Styrene, AMS, to aromatic ethenyl compounds such as hydroxyl-AMS, acenaphthylenes; (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) IBOA, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, (methyl) acrylic acid dihydro DCPA (dicyclopentenyl (meth) acrylate), (methyl) acrylic acid 4-hydroxylphenyl ester, to (methyl) acrylic ester such as oxirane modification (methyl) acrylic ester of cumyl phenol etc.In addition; Making the employed polymkeric substance with polymerizable unsaturated compound of carboxyl of resin glue (b-1), making in the polymkeric substance of the employed polymerizable unsaturated compound with Oxyranyle of resin glue (b-3), the polymerizable unsaturated compound that can make (methyl) acrylic acid 2-hydroxy methacrylate, glycerine list (methyl) acrylic ester etc. have hydroxyl carries out copolymerization.They can use multiple.

As the epoxy resin that is used to make resin glue (b-4), can enumerate epoxy resin that the reaction of epoxy resin, bisphenol f type epoxy resin, the alcohol hydroxyl group that passes through bisphenol f type epoxy resin and chloropropylene oxide that the reaction of bisphenol A type epoxy resin, the alcohol hydroxyl group through bisphenol A type epoxy resin and chloropropylene oxide gets gets, bisphenol-s epoxy resin, phenol type novalac epoxy, cresols type novalac epoxy, tris-phenol type epoxy resin, fluorenes epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin etc.In addition, can also use copoly type epoxy resin.

Make polymerizable unsaturated compound and acid anhydrides resin glue (b-4), that have carboxyl as being used to, can enumerate and employed polymerizable unsaturated compound and the same material of acid anhydrides in the manufacturing of above-mentioned resin glue (b-3).

As the multipolymer of making the employed styrene of resin glue (b-5) or its derivant and acid anhydrides, for example can enumerate styrene, meta-methoxy styrene, to the multipolymer of maleic acid list lower alkyl esters such as methoxy styrene etc. and maleic anhydride or monomethyl maleate, ethyl maleate, maleic acid list n-propyl, maleic acid list isopropyl ester, the positive butyl ester of maleic acid list, maleic acid list isobutyl ester, the maleic acid list tert-butyl ester.

Make polymerizable unsaturated compound resin glue (b-5), that have hydroxyl as being used to, for example can enumerate (methyl) acrylic acid hydroxyalkyl acrylate, N hydroxymethyl acrylamide, allyl alcohol etc.

In the present invention; As resin glue; Can use the polymkeric substance that has acidic functionality but do not have the polymerism unsaturated group individually, and, can also this polymkeric substance be used with the polymkeric substance with acidic functionality and polymerism unsaturated group.As having acidic functionality but do not have the object lesson of the polymkeric substance of polymerism unsaturated group, for example can enumerate disclosed multipolymers such as japanese kokai publication hei 7-140654 communique, japanese kokai publication hei 9-311444 communique, japanese kokai publication hei 10-31308 communique, japanese kokai publication hei 10-300922 communique, japanese kokai publication hei 11-174224 communique, japanese kokai publication hei 11-258415 communique, TOHKEMY 2000-56118 communique, TOHKEMY 2002-296778 communique, TOHKEMY 2004-101728 communique.

The acid number of the resin glue among the present invention is preferably 10～300KOH/mg, and more preferably 30～270KOH/mg further is preferably 50～250KOH/mg.Here in " acid number " expression with the mg number of the needed KOH of solid state component of 1g resin glue.

Resin glue of the present invention adopts gel permeation chromatography, and (GPC, eluting solvent: the weight-average molecular weight by polystyrene conversion that tetrahydrofuran) records (below be called " Mw ") is preferably 1,000～100,000, further is preferably 3,000～50,000.In this case, if Mw is too small, residual film ratio that then might the gained tunicle etc. reduce or pattern form, thermotolerance etc. are damaged or electrical characteristics worsen; On the other hand, if Mw is excessive, then might resolution reduce or pattern form damages or when utilizing the gap nozzle mode to be coated with, becomes and is easy to generate dry foreign matter.

In addition; The Mw of resin glue of the present invention and employing gel permeation chromatography (GPC; Eluting solvent: the ratio (Mw/Mn) of the number-average molecular weight by polystyrene conversion that tetrahydrofuran) records (below be called " Mn ") is preferably 1.0～5.0, and more preferably 1.0～3.0.

Resin glue of the present invention can adopt known method manufacturing, can also adopt that for example TOHKEMY 2003-222717 communique, TOHKEMY 2006-259680 communique, No. 07/029871 disclosed method such as pamphlet of International Publication are controlled its structure, Mw, Mw/Mn.In addition, above-mentioned polymkeric substance with acidic functionality and polymerism unsaturated group can adopt known method for example disclosed methods such as japanese kokai publication hei 5-19467 communique, japanese kokai publication hei 5-61196 communique, japanese kokai publication hei 6-230212 communique, japanese kokai publication hei 7-207211 communique, TOHKEMY 2008-181095 communique make.

In the present invention, resin glue can use individually or mix more than 2 kinds and use.

In the present invention, with respect to (A) colorant of 100 mass parts, the content of resin glue is preferably 10～1, and 000 mass parts further is preferably 20～500 mass parts.In this case, if the content of the binder resin is too small, for example, alkali developability may decrease, in the unexposed portion of the substrate or the light-shielding layer is generated on the residue, scum (ground dirt); hand, If too large, the relative concentration of the coloring agent is reduced, and thus the thin film may be difficult to achieve the target color density.

-(C) crosslinking chemical-

In the present invention, (C) crosslinking chemical is meant the compound with group of ability polymerization more than 2.As the group of ability polymerization, for example can enumerate ethylenic unsaturated group, Oxyranyle, oxetanyl, N-(alkoxymethyl)-2 amino etc.In the present invention, as (C) crosslinking chemical preferably have (methyl) acryloyl group more than 2 compound, or have the amino compounds of 2 above N-(alkoxymethyl)-2s.

As above-mentioned object lesson with compound of (methyl) acryloyl group more than 2, can enumerate the reaction of aliphatic polyhydroxy compound and (methyl) acrylic acid and multifunctional (methyl) acrylic ester of obtaining, through multifunctional (methyl) acrylic ester of caprolactone modification, react and polyfunctional carbamate (methyl) acrylic ester that obtains, (methyl) acrylic ester and anhydride reaction and multifunctional (methyl) acrylic ester of obtaining etc. with carboxyl with hydroxyl through multifunctional (methyl) acrylic ester of alkylene oxide modification, (methyl) acrylic ester and polyfunctional isocyanate with hydroxyl.

Here; As above-mentioned aliphatic polyhydroxy compound; For example can enumerate the aliphatic polyhydroxy compound of the binary as monoethylene glycol, propylene glycol, polyglycol, polypropylene glycol, the aliphatic polyhydroxy compound more than the ternary as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol.As above-mentioned (methyl) acrylic ester, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, trimethylolpropane two (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dimethyl allene acid glyceride etc. with hydroxyl.As above-mentioned polyfunctional isocyanate, for example can enumerate toluene diisocyanate, hexamethylene diisocyanate, diphenyl methylene isocyanates, IPDI etc.As acid anhydrides; For example can enumerate the acid anhydrides of the dibasic acid as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, the tetra-atomic acid dianhydride as pyromellitic acid dianhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic acid dianhydride.

In addition, as above-mentioned multifunctional (methyl) acrylic ester, for example can enumerate the compound that [0015]～[0018] paragraph of japanese kokai publication hei 11-44955 communique is put down in writing through caprolactone modification.As above-mentioned multifunctional (methyl) acrylic ester, can enumerate oxirane and/or three (methyl) acrylic ester of epoxy pronane modification, the oxirane of pentaerythrite and/or four (methyl) acrylic ester of epoxy pronane modification, oxirane and/or five (methyl) acrylic ester of epoxy pronane modification, the oxirane of dipentaerythritol and/or six (methyl) acrylic ester of epoxy pronane modification etc. of dipentaerythritol of three (methyl) acrylic ester, pentaerythrite of oxirane and/or epoxy pronane modification of three (methyl) acrylic ester, trimethylolpropane of oxirane and/or epoxy pronane modification of two (methyl) acrylic ester, the isocyanuric acid of oxirane and/or the epoxy pronane modification of bisphenol-A through the alkylene oxide modification.

In addition, have amino compounds of 2 above N-(alkoxymethyl)-2s, for example can enumerate compound with melamine structure, benzoguanamine structure, urea structure etc. as above-mentioned.In addition, melamine structure, benzoguanamine structure are meant that having 1 above triazine ring or phenyl replaces the chemical constitution of triazine ring as basic framework, are the notions that also comprises melamine, benzoguanamine or their condensation product.As the object lesson of compound, can enumerate N, N, N ', N '; N with 2 above N-(alkoxymethyl)-2 amino ", N " and-six (alkoxy methyl) melamine, N, N, N '; N '-four (alkoxy methyl) benzoguanamine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc.

Among these crosslinking chemicals, preferably make the above aliphatic polyhydroxy compound of ternary with the reaction of (methyl) acrylic acid and multifunctional (methyl) acrylic ester, multifunctional (methyl) acrylic ester through caprolactone modification, polyfunctional carbamate (methyl) acrylic ester that obtains, multifunctional (methyl) acrylic ester, N, N with carboxyl; N ', N ', N "; N "-six (alkoxy methyl) melamine, N; N, N ', N '-four (alkoxy methyl) benzoguanamine.On excellent and unexposed the substrate of surface smoothing property high from the intensity of dyed layer, dyed layer and light shield layer be difficult for producing aspects such as scum, film be residual and consider; Among multifunctional (methyl) acrylic ester that the aliphatic polyhydroxy compound that makes more than the ternary obtains with the reaction of (methyl) acrylic acid, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate; Have among multifunctional (methyl) acrylic ester of carboxyl, especially preferably make the reaction of pentaerythritol triacrylate and succinic anhydride and the compound, dipentaerythritol five acrylic ester that obtain react with succinic anhydride and the compound that obtains.In the present invention, (C) crosslinking chemical can use separately or mix more than 2 kinds and use.

With respect to (B) resin glue of 100 mass parts, the content of (C) crosslinking chemical among the present invention is 10～1,000 mass parts preferably, preferred especially 20～500 mass parts.In this case, if the content of crosslinking chemical is very few, then enough curable might can't be obtained.On the other hand; If the content of crosslinking chemical is too much; Then when giving alkali development, can have that alkali development reduces, on unexposed the substrate or become on the light shield layer and be easy to generate residual etc. the trend of scum, film to colored radiation-sensitive composition of the present invention.

-(D) Photoepolymerizationinitiater initiater-

In the present invention, Photoepolymerizationinitiater initiater is meant through utilizing above-mentioned ultraviolet LED to make public to produce the compound of the spike of the polymerization that can cause above-mentioned (C) crosslinking chemical.

As such Photoepolymerizationinitiater initiater, for example can enumerate thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound,

salt based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, encircle quinone based compound, diazonium based compound, acid imide sulphonate based compound etc. more.In the present invention, Photoepolymerizationinitiater initiater can use separately or two or more mixing use.As Photoepolymerizationinitiater initiater, be preferably selected from least a in thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, the O-acyl group oxime compound.

Among the preferred Photoepolymerizationinitiater initiater of the present invention; Object lesson as the thioxanthones based compound; Can enumerate thioxanthones, 2-clopenthixal ketone, 2-methyl thioxanthones, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-dimethyl thioxanthones, 2; 4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.

In addition; As the object lesson of above-mentioned acetophenone based compound, can enumerate 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl) butane-1-ketone etc.

In addition, as the object lesson of above-mentioned bisglyoxaline based compound, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 '; 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4; The 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In addition, when using the bisglyoxaline based compound, consider from improving this point of sensitivity as Photoepolymerizationinitiater initiater, preferred and use hydrogen donor.Said here " hydrogen donor " is meant the compound that can supply with hydrogen atom to the free radical that is produced by the bisglyoxaline based compound through exposure.As hydrogen donor; For example can enumerate mercaptan such as 2-mercaptobenzothiazole, 2-sulfydryl benzo

azoles is hydrogen donor, 4; Amine such as 4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone are hydrogen donor.In the present invention, hydrogen donor can use separately or two or more mixing is used, but considers from can further improving this point of sensitivity, is that hydrogen donor and the amine more than a kind are that the hydrogen donor combination is used with the mercaptan more than a kind preferably.

In addition, as the object lesson of above-mentioned triazine based compound, can enumerate 2; 4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4; Two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4; Two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4; Two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4; Two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine etc. of 6-have the triazine based compound of halogenated methyl.

In addition; Object lesson as O-acyl group oxime compound; Can enumerate 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-{9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base]-9H-carbazole-3-yl }-1-(O-acetyl oxime) etc.As the commercially available article of O-acyl group oxime compound, can also enumerate NCI-831, NCI-930 (above is Asahi Denka Co., Ltd.'s corporate system) etc.

In the present invention, during Photoepolymerizationinitiater initiater beyond using the bisglyoxaline based compound of acetophenone based compound etc., also can and use sensitizer.As such sensitizer; For example can enumerate 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2, two (the 4-lignocaine benzal) cyclohexanone of 5-, 7-lignocaine-3-(4-lignocaine benzoyl) cumarin, 4-(lignocaine) chalcone etc.

In the present invention, the content of Photoepolymerizationinitiater initiater is preferably 0.01～120 mass parts with respect to (C) crosslinking chemical of 100 mass parts, is preferably 1～100 mass parts especially.In this case, if the content of Photoepolymerizationinitiater initiater is very few, the curing that then utilizes exposure to carry out probably is insufficient.If too much on the other hand, the trend that then can exist formed dyed layer when developing, to become and come off from substrate easily.

-solvent-

Colored radiation-sensitive composition of the present invention contains above-mentioned (A)～(D) composition, reaches other composition that adds arbitrarily, cooperates solvent to be prepared into liquid composition usually.As above-mentioned solvent, so long as will constitute that (A)～(D) composition, other composition of colored radiation-sensitive composition disperse or dissolving and not with these compositions reactions, volatile solvent with appropriateness, just can suitably select use.

In the present invention; As preferred solvent; For example can enumerate propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl butyl ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1; 3-butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid or ethyl pyruvate etc.

In the present invention, solvent can use separately or mix more than 2 kinds and use.

-other composition-

Colored radiation-sensitive composition of the present invention can also further contain other composition.As other composition, for example can enumerate the polyurethane series spreading agent, polyethyleneimine is that spreading agent, polyoxyethylene alkyl ether are that spreading agent, polyoxyethylene alkyl phenyl ether are that spreading agent, polyethylene glycol di are that spreading agent, fatty acid esters of sorbitan are that spreading agent, polyester are spreading agents such as spreading agent, acrylic acid series spreading agent; Fluorine is that surfactant, silicon are surfactants such as surfactant; Driving fit promoter such as vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy methyl dimethoxysilane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.

< display element >

Display element of the present invention possesses the color filter that adopts said method to make.As the concrete example of display element, can enumerate color liquid crystal display device, organic EL display element or Electronic Paper etc.

Possess that to adopt the color liquid crystal display device of the color filter that method of the present invention makes can be following structure for example: the driving of disposing thin film transistor (TFT) (Thin Film Transistor:TFT) is opposed by liquid crystal layer with other substrate Jie of substrate and the color filter that is provided with this embodiment.Perhaps color liquid crystal display device also can be following structure: (Indium Tin Oxide: the indium oxide of the tin that mixed) substrate of electrode is situated between opposed by liquid crystal layer with being formed with ITO at the substrate that disposes the color filter that is formed with this embodiment on the surface of driving with substrate of thin film transistor (TFT) (TFT).The latter's structure can make aperture opening ratio significantly improve, and has the such advantage of liquid crystal display cells that obtains bright and high-resolution.

Color liquid crystal display device possesses backlight unit.As backlight unit, for example can use the backlight unit of the structure that has made up cathode fluorescent tube fluorescent tubes such as (CCFL:Cold Cathode Fluorescent Lamp) and scatter plate.And, can also use with the backlight unit of White LED as light source.As White LED; For example can enumerate the White LED that red LED, green LED and blue led combination is obtained white light through colour mixture; Blue led, red LED and green-emitting phosphor combination are obtained the White LED of white light through colour mixture; Blue led, red light-emitting phosphor and the combination of green emitting fluorophor are obtained the White LED of white light through colour mixture; Through blue led and YAG is the White LED that the colour mixture of fluorophor obtains white light; Blue led, orange luminescence fluorophor and green emitting fluorophor are made up the White LED that obtains white light through colour mixture, ultraviolet LED, red light-emitting phosphor, green emitting fluorophor and blue-light-emitting fluorescent material combination are obtained the White LED of white light etc. through colour mixture.

For possessing the color liquid crystal display device that adopts the color filter that method of the present invention makes; Can use TN (Twisted Nematic; Twisted-nematic) type, STN (Super Twisted Nematic, supertwist is to row) type, IPS (In-Planes Switching, face intra) type, VA (Vertical Alignment; Vertical orientated) suitable liquid crystal mode such as type, OCB (Optically Compensated Birefringence, optical compensation curved arrangement) type.

Have and adopt organic EL display element of the color filter that method of the present invention makes to adopt suitable structure, for example can enumerate disclosed structure in the japanese kokai publication hei 11-307242 communique.

Have and adopt the Electronic Paper of the color filter that method of the present invention makes to adopt suitable structure, for example can enumerate disclosed structure in the TOHKEMY 2007-41169 communique.

More than, this embodiment is illustrated, but the present invention is not limited to above-mentioned embodiment, can in the scope that does not break away from purport, carry out various distortion and implement.

Embodiment

Below, enumerate embodiment, embodiment of the present invention further is described particularly.But the present invention is not limited to following embodiment.

(preparations of pigment dye mixed liquor etc.)

Preparation example 1

Will as C.I. naphthol green 58/C.I. solvent yellow 179=60/40 (mass ratio) potpourri 15 mass parts of colorant, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare pigment dye mixed liquor (A1).

Preparation example 2

Will as C.I. naphthol green 58/C.I. solvent yellow 179=80/20 (mass ratio) potpourri 15 mass parts of colorant, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare pigment dye mixed liquor (A2).

Preparation example 3

Will be as the C.I. pigment blue 15 of colorant: 6/C.I. Blue 7=60/40 (mass ratio) potpourri 15 mass parts, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare pigment dye mixed liquor (A3).

Preparation example 4

Will be as the C.I. pigment blue 15 of colorant: 6/C.I. Blue 7=80/20 (mass ratio) potpourri 15 mass parts, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare pigment dye mixed liquor (A4).

Preparation example 5

Will as C.I. naphthol green 58/C.I. pigment yellow 150=60/40 (mass ratio) potpourri 15 mass parts of colorant, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare dispersible pigment dispersion (A5).

Preparation example 6

Will be as the C.I. pigment blue 15 of colorant: 6/ xanthene based dye C.I. rhodamine 6G=60/40 (mass ratio) potpourri, 15 mass parts, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare pigment dye mixed liquor (A6).

Preparation example 6

Will be as the C.I. pigment blue 15 of colorant: the triarylmethane that 6/ following formula is represented be that mordant pigment is (in the formula; X=1～2)=60/40 (mass ratio) potpourri 15 mass parts, as the BYK-LPN21116 (BYK corporate system) of 10 mass parts (nonvolatile component=40 quality %) of spreading agent, as the propylene glycol methyl ether acetate of 75 mass parts of solvent through ball mill mixed and dispersed 12 hours, prepare dispersible pigment dispersion (A7).

(synthesizing of resin glue)

Synthetic example 1

In the flask that possesses condenser pipe and stirrer, add 2 of 2 mass parts; The propylene glycol methyl ether acetate of 2 '-azoisobutyronitrile and 200 mass parts; Then add N-phenylmaleimide, 55 mass parts of methacrylic acid, 20 mass parts of 15 mass parts benzyl methacrylate, 10 mass parts styrene and 3 mass parts as 2 of molecular weight regulator; 4-diphenyl-4-methyl-1-pentene (Japanese grease (strain) system trade name: Nofmer MSD), carry out nitrogen replacement.Afterwards, stir lentamente, make the temperature of reaction solution rise to 80 ℃, keep this temperature to carry out polymerization in 5 hours, obtained resin solution (solid component concentration=33 quality %) thus.Gained resin M w=16,000, Mn=7,000.With this resin solution as " resin glue solution (B1) ".

Synthetic example 2

In the flask that possesses condenser pipe and stirrer; The N-phenylmaleimide to vinyl benzyl glycidol ether, 40 mass parts of 44 mass parts, the benzyl methacrylate of 16 mass parts are dissolved in the propylene glycol methyl ether acetate of 300 mass parts; Further add 2 of 8 mass parts; 2 of 2 '-azoisobutyronitrile and 8 mass parts, 4-diphenyl-4-methyl-1-pentene carries out nitrogen replacement.Afterwards, when stirring lentamente, the limit is carried out the nitrogen bubble limit reaction solution is warming up to 80 ℃, keeps this temperature to carry out polymerization in 5 hours.

Then, in this solution, add methacrylic acid, the p methoxy phenol of 0.5 mass parts and the TBAB of 4.4 mass parts of 17 mass parts, under 120 ℃ temperature, carry out reaction in 9 hours.The succinic anhydride that further adds 18.5 mass parts is after carrying out reaction in 6 hours under 100 ℃ the temperature; The reaction solution temperature is remained on 85 ℃ directly washes 2 times; Carry out concentrating under reduced pressure, obtained resin glue solution (solid component concentration=33 quality %) thus.Gained resin glue Mw=7,800, Mn=5,000.With this resin glue solution as " resin glue solution (B2) ".

Synthetic example 3

In the flask that possesses condenser pipe and stirrer; The 3-methacryloxy methyl-3-ethyl oxetanes of 25 mass parts, the methacrylic acid of 18 mass parts, mono succinate [the 2-acryloxy ethyl] ester of 9 mass parts, the N-phenylmaleimide of 10 mass parts, the benzyl methacrylate of 24 mass parts, the methacrylic acid hydroxyl ethyl ester of 14 mass parts are dissolved in the propylene glycol methyl ether acetate of 300 mass parts; Further add 2 of 6 mass parts; 2 of 2 '-azoisobutyronitrile and 6 mass parts; 4-diphenyl-4-methyl-1-pentene afterwards, carries out 15 minutes purging with nitrogen gas.After the purging with nitrogen gas, limit stirring reaction liquid and nitrogen bubble limit are heated to 80 ℃, carry out polymerization 5 hours.

In the copolymer solution of 200 mass parts of gained, add the 2-methacryloxyethyl isocyanates of 13.4 mass parts, the 4-metoxyphenol as polymerization inhibitor of 0.2 mass parts, make its reaction 2 hours at 90 ℃.This reactant liquor with ion exchange water washing 2 times, is carried out concentrating under reduced pressure, obtained resin glue solution (solid component concentration=33 quality %) thus.Gained resin glue Mw=11,000, Mn=5,800.With this resin glue solution as " resin glue solution (B3) ".

Synthetic example 4

In the flask that possesses condenser pipe and stirrer; The N-phenylmaleimide of 30 mass parts, the methacrylic acid of 20 mass parts, the styrene of 20 mass parts, the benzyl methacrylate of 30 mass parts are dissolved in the cyclohexanone of 200 mass parts; Further add 2 of 3 mass parts; 2 of 2 '-azoisobutyronitrile, 2 mass parts, 4-diphenyl-4-methyl-1-pentene carries out 15 minutes purging with nitrogen gas afterwards.After the purging with nitrogen gas, limit stirring reaction liquid and nitrogen bubble limit are heated to 80 ℃, carry out polyase 13 hour.

In the copolymer solution of 60 mass parts of gained; Add the 4-metoxyphenol of 0.2 mass parts, the etamon chloride of 0.2 mass parts, the cyclohexanone of 40 mass parts; Further add the acrylic acid 3 of 2.1 mass parts, 4-epoxycyclohexyl methyl esters makes its reaction 30 hours at 90 ℃.For this reactant liquor, the liquid temperature is remained on 80 ℃ directly wash 2 times, carry out concentrating under reduced pressure, obtained resin glue solution (solid component concentration=33 quality %) thus.Gained resin glue Mw=16,200, Mn=6,500.With this resin glue solution as " resin glue solution (B4) ".

Embodiment 1

(preparation of colored radiation-sensitive composition)

The Nippon Kayaku K. K as the system KAYARAD MAX-3510 (potpourris of dipentaerythritol acrylate and dipentaerythritol five acrylic ester) of Nippon Kayaku K. K of crosslinking chemical and 6 mass parts of the pigment dye mixed liquor (A1) of 100 mass parts, the resin glue solution (B1) as resin glue of 18 mass parts (solid component concentration=33 quality %), 6 mass parts is made (the 4-morpholinyl phenyl) butane-1-ketone of the 2-benzyl-2-dimethylamino-1-as Photoepolymerizationinitiater initiater and 3 mass parts of KAYARAD DPCA-60 (caprolactone modification dipentaerythritol acrylate), 1 mass parts ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 0.2 mass parts be that Dainippon Ink Chemicals of surfactant makes MEGAFAC F-554 and mixes as the propylene glycol methyl ether acetate of solvent as fluorine, be the green radiation-ray sensitive composition of 15 quality % thereby be prepared into solid component concentration.

(formation of pattern of pixels and the evaluation of color stability)

After being coated on the glass substrate with the slot die coating machine the green radiation-ray sensitive composition of gained, on 90 ℃ heating plate, carry out prebake in 4 minutes, having formed thickness is filming of 2 μ m.

Then, after will being formed with the substrate of filming and being cooled to room temperature, use peak wavelength as the ultraviolet LED of 365nm, be situated between by the striated photomask, with 2 000J/m ²Exposure make public to filming.Afterwards, at 1kgf/cm ²The developer solution that forms to 0.04 quality % potassium hydroxide aqueous solution of 23 ℃ of the substrate of gained ejections under the development pressure of (nozzle diameter is 1mm) carries out 1 minute spray thus and develops.Afterwards, air-dry with this substrate of ultrapure water washing, thus on substrate, formed green striated pattern of pixels.

For filming and formed pattern of pixels before the exposure, adopt color analysis appearance (chiseling electronics (strain) system MCPD2000 greatly) to measure dichroism, thereby try to achieve aberration (Δ E*ab).Evaluation result is shown in table 1.

Embodiment 2～13

In embodiment 1, the kind of each composition and content by changing shown in the table 1, in addition, are likewise prepared each colored radiation-sensitive composition with embodiment 1.Then,, exposure condition setting is become as shown in table 1, in addition, likewise form pattern of pixels, carry out the evaluation of color stability with embodiment 1 with the colored radiation-sensitive composition of gained.Evaluation result is shown in table 1.

Comparative example 1～6 and reference example 1～2

In embodiment 1, the kind of each composition and content by changing shown in the table 2, in addition, are likewise prepared each colored radiation-sensitive composition with embodiment 1.Then,, exposure condition setting is become as shown in table 2, in addition, likewise form pattern of pixels, carry out the evaluation of color stability with embodiment 1 with the colored radiation-sensitive composition of gained.Evaluation result is shown in table 2.

[table 2]

In table 1 and table 2, each composition is described below.

C1: caprolactone modification dipentaerythritol acrylate (Nippon Kayaku K. K's system, trade name KAYARAD DPCA-60)

C2: the potpourri (Toagosei Co., Ltd's system, trade name TO-1382) of the mono-esterification thing of dipentaerythritol five acrylic ester and succinic acid, dipentaerythritol acid ester and dipentaerythritol five acrylic ester

C3: the potpourri of dipentaerythritol acrylate and dipentaerythritol five acrylic ester (Nippon Kayaku K. K's system, trade name KAYARAD MAX-3510)

C4: oxirane oligomer modification dipentaerythritol acrylate (Nippon Kayaku K. K's system, trade name KAYARAD DPEA-12)

D1:2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone (Ciba Specialty Chemicals corporate system, trade name Irgacure369)

D2: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (Ciba Specialty Chemicals corporate system, trade name IRGACUREOXE02)

The D3:2-mercaptobenzothiazoler

D4:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline (Baotugu Chemical Industrial Co., Ltd's system, trade name B-CIM)

D5:2,4-diethyl thioxanthone (Nippon Kayaku K. K's system, trade name CAYACURE DETX-S)

D6:4,4 '-two (diethylamino) benzophenone

D7: Asahi Denka Co., Ltd., trade name NCI-930.

Claims (7)

1. the formation method of a pattern of pixels is characterized in that, comprising:

(1) operation of filming of formation colored radiation-sensitive composition on substrate, said colored radiation-sensitive composition contains at least a kind that is selected from dyestuff and the mordant pigment; And

(2) operation that adopts ultraviolet LED that said at least a portion of filming is made public.

2. formation method according to claim 1, wherein, the ultraviolet peak wavelength that said ultraviolet LED sends is more than 300nm.

3. formation method according to claim 1, wherein, said colored radiation-sensitive composition contains that to be selected from azo based dye, triarylmethane based dye, xanthene based dye, methine based dye and triarylmethane be at least a kind in the mordant pigment.

4. formation method according to claim 1, wherein, said colored radiation-sensitive composition contains the resin glue with acidic functionality and polymerism unsaturated group.

5. a color filter is characterized in that, possesses the pattern of pixels that adopts each described method in the claim 1～4 and form.

6. a display element is characterized in that, possesses the described color filter of claim 5.

7. a colored radiation-sensitive composition is characterized in that, contains: (A) contain at least a kind colorant being selected from dyestuff and the mordant pigment, (B) resin glue, (C) crosslinking chemical and (D) Photoepolymerizationinitiater initiater;

Said colored radiation-sensitive composition is used for making public through ultraviolet LED and forms pattern of pixels.